The number and importance of polyquinane natural products continues to grow and a diverse range of biological activities have been identified. The proposal outlines the continued development of a general strategy toward this class of compounds which permits entry to both natural products and synthetic analogues of widely differing structural types. The main focus of the proposal is on the development of new free radical-based methods for carbon-carbon bond formation. The unique ability to sequence free radical reactions to form several C-C bonds in one step is highlighted and a variety of new methods based on this concept are proposed. In all cases, the new chemistry to be developed is illustrated in the context of the synthesis of one or more important natural products, although more general utility is always implied. New methods to generate radicals and control both regio- and stereoselectivity in radical reactions are also proposed. The chemistry outlined int his proposal will contribute both to the understanding of free radical reactions and to the ability to prepare important cyclopentanoid natural products.